CN101653114A - Hydroxyl apatite pesticide and fertilizer slow release complex prepared by one step synthesis - Google Patents
Hydroxyl apatite pesticide and fertilizer slow release complex prepared by one step synthesis Download PDFInfo
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- CN101653114A CN101653114A CN200910067226A CN200910067226A CN101653114A CN 101653114 A CN101653114 A CN 101653114A CN 200910067226 A CN200910067226 A CN 200910067226A CN 200910067226 A CN200910067226 A CN 200910067226A CN 101653114 A CN101653114 A CN 101653114A
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Abstract
The invention discloses a one step synthesis method for preparing hydroxyl apatite pesticide and fertilizer slow release complex, including the following steps: fertilizer or pesticide is dissolved inphosphate solution, calcium salt solution is slowly dropped in and continuous stirring is carried out, the obtained mixed solution is centrifuged, and sediment after centrifugation is dried at certain temperature, so as to obtain the complex. One step synthesis method is adopted to embed the pesticide and chemical fertilizer into internal grid of HAP, step-by-step release of nutrient in the pesticide and fertilizer can be realized, sudden release action is avoided, so that pesticide effect is long and the problem that crop death or active ingredient drain caused by aggregation of massive nutrients can be avoided. As HAP has the characteristic of biological degradability, the obtained products after degradation are phosphate radical ion and calcium ion, the substances are not only environmentally friendly but also can be used as nutrients for crop, and long-term use can improve soil environment.
Description
Technical field
The present invention relates to the preparation method of a kind of agricultural chemicals, slow-release fertilizer compound, especially disclose a kind of one-step synthesis and prepared hydroxyapatite pesticide, slow-release fertilizer compound, belong to the agriculture chemical production technical field.
Background technology
The sustained release agent of agricultural chemicals, chemical fertilizer can prolong the lasting period of same dose agricultural chemicals greatly, and the access times of minimizing agricultural chemicals, chemical fertilizer and total consumption make residual and contamination of heavy significantly reduces, and also reduce the toxicity and the poisoning of agricultural chemicals, chemical fertilizer.
The preparation method of existing agricultural chemicals, slow-release fertilizer agent is based on coating, coating, support methods.Used coated fertilizer such as pitch, paraffin, sulphur etc., this method production process complexity, cost is higher, insoluble entry own, the drug difficulty, and long-term use can cause soil acidification, the destruction soil structure; And commonly used before in the support methods as conduct bonding carriers such as sepiolite, clay, bentonite, diatomite, agricultural chemicals, chemical fertilizer are adsorbed in its surperficial duct, and the product load capacity of this method preparation is limited, and the prominent phenomenon of releasing is arranged; So the present invention adopts one-step synthesis that agricultural chemicals, chemical fertilizer are embedded in hydroxyapatite inside, not only increased load capacity greatly, can also reach the purpose that slowly-releasing discharges.
Summary of the invention
The present invention discloses a kind of one-step synthesis and prepares hydroxyapatite pesticide, fertilizer slow release complex, and the prominent phenomenon of releasing appears in slow release complex easily that solved existing the type.
One-step synthesis of the present invention prepares hydroxyapatite pesticide, fertilizer slow release complex, may further comprise the steps:
Chemical fertilizer or agricultural chemicals are dissolved in the phosphate solution, calcium salt soln are slowly splashed into again and constantly stir, the gained mixed solution is centrifugal again, and being deposited under the uniform temperature after centrifugal is dry and obtain compound.
Above-mentioned method, concrete steps are as follows:
Solution A preparation: take by weighing 0.1～5.5mol/L calcium salt soln, 5～20ml, shake up standby;
Solution B preparation: take by weighing phosphate solution 25～100ml of 0.1～5.5mol/L, regulate the pH value between 6.5～11.0, shake up standby with concentrated ammonia liquor;
Solution A is 1.67 with the Ca/P ratio of solution B;
Take by weighing starting material 25～500mg, the solution B dissolving is slowly stirred; Solution A is added drop-wise in the solution B gradually again, keeps temperature of reaction system between 37 ℃～60 ℃, the pH value slowly stirred 1～3 hour between 6.5～11.0; 10000rpm/min is centrifugal 10～20 minutes under the reactant liquor room temperature; Drying is 24～72 hours under the centrifuged deposit room temperature, and products therefrom is in 4 ℃ of preservations.
Calcium salt is selected from above-mentioned method: any in calcium acetate, nitrate of lime, calcium carbonate, calcium chloride, slaked lime, the calcium oxide.
Phosphate is selected from above-mentioned method: any one or more in ammonium dihydrogen phosphate (ADP), diammonium hydrogen phosphate, ammonium acetate, sodium dihydrogen phosphate, potassium dihydrogen phosphate, dipotassium hydrogen phosphate, phosphoric acid, the sodium phosphate.
The starting material that said method relates to is any in nitrogenous fertilizer, phosphate fertilizer, potash fertilizer and compound fertilizer thereof or the mixed fertilizer.
Starting material also can be: any in mineral sources agricultural chemicals, biogenic pesticide and the chemical pesticide.
The used bonding carrier (hydroxyapatite) of the present invention is owing to be nano level carrier, thus have very big specific surface area, thereby stronger absorption and bearing capacity are arranged; In dispose procedure, be adsorbed on the outside duct of HAP agricultural chemicals before this, chemical fertilizer discharges earlier, the degraded along with HAP discharges inner material gradually then, thereby reaches slow releasing function.
Good effect of the present invention is: adopt one-step synthesis agricultural chemicals, chemical fertilizer to be embedded in the inner mesh of HAP, can realize the progressively release of nutrient in agricultural chemicals, the fertilizer, avoid it to dash forward and released effect, make drug effect permanent, can not cause crop death or active ingredient losing issue because of a large amount of gatherings of nutrient.Because HAP has biodegradable characteristics, degraded back products therefrom is phosphate anion and calcium ion, and these materials are environmental sound not only, also can be used as nutrient and gives crop, and long-term use can also improve soil environment.
Description of drawings:
Fig. 1 is a HAp-agricultural chemicals compound stereoscan photograph;
Fig. 2 is a HAp-agricultural chemicals compound transmission electron microscope photo;
Fig. 3 is infared spectrum a.HAp; B. agricultural chemicals; C.HAp-agricultural chemicals compound;
Fig. 4 is an X-ray diffracting spectrum;
Fig. 5 is different embodiment gained compounds cumulative release curves in water.
Embodiment
For the ease of understanding the present invention, especially exemplified by following examples.Its effect is understood that it is to explaination of the present invention but not to any type of restriction of the present invention.
Solution A preparation: accurately take by weighing anhydrous acetic acid calcium 0.705g, add redistilled water and be settled to 10ml, shake up standby;
The solution B preparation: accurately take by weighing ammonium dihydrogen phosphate (ADP) 1.381g, ammonium acetate 4.008g adds redistilled water 45ml, regulates the pH value about 7.6 with concentrated ammonia liquor, adds redistilled water and is settled to 50ml, shakes up standby;
Accurately take by weighing urea 300mg, be dissolved in the solution B (50ml), slowly be stirred to dissolving fully; Again solution A (10ml) is added drop-wise in the solution B gradually, slowly stirred 2 hours; Centrifugal 15 minutes of reactant liquor 10000rpm/min under room temperature; Centrifuged deposit at room temperature dry 48 hours, 4 ℃ of preservations.
Embodiment 2
Solution A preparation: accurately take by weighing anhydrous acetic acid calcium 0.705g, add redistilled water and be settled to 10ml, shake up standby;
The solution B preparation: accurately take by weighing ammonium dihydrogen phosphate (ADP) 1.381g, ammonium acetate 4.008g adds redistilled water 45ml, regulates the pH value about 7.6 with concentrated ammonia liquor, adds redistilled water and is settled to 50ml, shakes up standby;
Accurately take by weighing Avermectin 50mg, be dissolved in the solution B (50ml), slowly stir; Solution A (10ml) is added drop-wise in the solution B gradually, slowly stirred 1 hour; Centrifugal 15 minutes of reactant liquor 10000rpm/min under room temperature; Centrifuged deposit at room temperature dry 48 hours gets the Avermectin compound, 4 ℃ of preservations.Sign is seen Fig. 1～Fig. 4.
Embodiment 3
Solution A preparation: accurately take by weighing nitrate of lime 1.321g, add redistilled water and be settled to 10ml, shake up standby;
Solution B preparation: accurately take by weighing ammonium phosphate 0.362g, add redistilled water 45ml, regulate the pH value about 8.6, add redistilled water and be settled to 50ml, shake up standby with concentrated ammonia liquor;
Accurately take by weighing potassium sulphate 200mg, be dissolved in the solution B (50ml), slowly be stirred to dissolving fully; Again solution A (10ml) is added drop-wise in the solution B gradually, slowly stirred 2 hours; Centrifugal 12 minutes of reactant liquor 12000rpm/min under room temperature; Centrifuged deposit at room temperature dry 72 hours, 4 ℃ of preservations.
Embodiment 4
Solution A preparation: accurately take by weighing nitrate of lime 0.759g, add redistilled water and be settled to 50ml, shake up standby;
Solution B preparation: accurately take by weighing diammonium hydrogen phosphate 0.195g, add redistilled water 245ml, regulate the pH value about 9.0, add redistilled water and be settled to 500ml, shake up standby with concentrated ammonia liquor;
Accurately take by weighing calcium phosphate 400mg, be dissolved in the solution B (500ml), slowly be stirred to dissolving fully; Again solution A (50ml) is added drop-wise in the solution B gradually, slowly stirred 2 hours; Centrifugal 10 minutes of reactant liquor 13000rpm/min under room temperature; Centrifuged deposit at room temperature dry 48 hours, 4 ℃ of preservations.
Embodiment 5
Solution A preparation: accurately take by weighing nitrate of lime 0.759g, add redistilled water and be settled to 10ml, shake up standby;
Solution B preparation: accurately take by weighing diammonium hydrogen phosphate 0.195g, add redistilled water 45ml, regulate the pH value about 10.0, add redistilled water and be settled to 50ml, shake up standby with concentrated ammonia liquor;
Accurately take by weighing tribenuron-methyl 50mg, be dissolved in the solution B (50ml) that has prepared, slowly stir; The solution A of having prepared (10ml) is added drop-wise in the solution B gradually, slowly stirred 2 hours; Reactant liquor was in centrifugal 12 minutes of 40 ℃ of following 13000rpm/min; Centrifuged deposit at room temperature dry 48 hours, 4 ℃ of preservations.
Embodiment 6
Solution A preparation: accurately take by weighing calcium carbonate 0.654g, add redistilled water and be settled to 50ml, shake up standby;
Solution B preparation: accurately take by weighing diammonium hydrogen phosphate 0.518g, add redistilled water 245ml, regulate the pH value about 7.4, add redistilled water and be settled to 500ml, shake up standby with concentrated ammonia liquor;
Accurately take by weighing zinc fertilizer 100mg, be dissolved in the solution B (500ml) that has prepared, slowly stir; The solution A of having prepared (50ml) is added drop-wise in the solution B gradually, slowly stirred 2 hours; Centrifugal 13 minutes of reactant liquor 11000rpm/min under room temperature; Centrifuged deposit at room temperature dry 48 hours, 4 ℃ of preservations.
Embodiment 7
Solution A preparation: accurately take by weighing calcium carbonate 0.654g, add redistilled water and be settled to 10ml, shake up standby;
Solution B preparation: accurately take by weighing diammonium hydrogen phosphate 0.518g, add redistilled water 45ml, regulate the pH value about 9.0, add redistilled water and be settled to 50ml, shake up standby with concentrated ammonia liquor;
Accurately take by weighing copper sulphate 50mg, be dissolved in the solution B (50ml), slowly stir; Again solution A (10ml) is added drop-wise in the solution B gradually, slowly stirred 2 hours; Centrifugal 12 minutes of reactant liquor 13000rpm/min under room temperature; Centrifuged deposit at room temperature dry 48 hours, promptly.
The test example
Take by weighing hydroxyapatite/thiourea slow release fertilizer 5.5g of embodiment 1, clean again with distilled water, the 500g quartz sand that 20 mesh sieve holes are crossed in dry back mixes, in the chromatographic column of packing into, make its filling degree of tightness appropriateness, splash into distilled water then, dripping speed is 0.5ml/min, collects liquid with receiver, 10 receivers are set altogether, each receiver is collected 20min (about altogether 10.0ml), gets liquid 1.00ml again from each receiver, adds the 3ml concentrated sulfuric acid and digests, distill with the semimicro azotometer then, absorb with 2% boric acid,, the results are shown in Table 1 with 0.040N HCl titration.
Experimental data shows, compares with the urea that routine is used, and uses this fertilizer, and its leaching speed reduces more than one times, has reached the slowly-releasing purpose.The use of this fertilizer has positive role and realistic meaning to preserving the ecological environment, implementation process is economized fertile saving of labor simultaneously.
The nitrogen content variation table of comparisons in urea and the slow release fertilizer under the table 1 simulation rain drop erosion condition
The comparison of the different embodiment gained of table 2 slow release fertilizer slow release effect in soil
Claims (6)
1, a kind of one-step synthesis for preparing hydroxyapatite pesticide, fertilizer slow release complex, may further comprise the steps: chemical fertilizer or agricultural chemicals are dissolved in the phosphate solution, again calcium salt soln is slowly splashed into and constantly stir, the gained mixed solution is centrifugal again, and being deposited under the uniform temperature after centrifugal is dry and obtain compound.
2, the described method of claim 1, concrete steps are as follows:
Solution A preparation: take by weighing 0.1～5.5mol/L calcium salt soln, 5～20ml, shake up standby;
Solution B preparation: take by weighing phosphate solution 25～100ml of 0.1～5.5mol/L, regulate the pH value between 6.5～11.0, shake up standby with concentrated ammonia liquor;
Solution A is 1.67 with the Ca/P ratio of solution B;
Take by weighing starting material 25～500mg, the solution B dissolving is slowly stirred; Solution A is added drop-wise in the solution B gradually again, keeps temperature of reaction system between 37 ℃～60 ℃, the pH value slowly stirred 1～3 hour between 6.5～11.0; 10000rpm/min is centrifugal 10～20 minutes under the reactant liquor room temperature; Drying is 24～72 hours under the centrifuged deposit room temperature, and products therefrom is in 4 ℃ of preservations.
3, method according to claim 1 and 2 is characterized in that: calcium salt is selected from any in calcium acetate, nitrate of lime, calcium carbonate, calcium chloride, slaked lime, the calcium oxide.
4, according to claims 1 or 2 described methods, it is characterized in that: phosphate is selected from any one or more in ammonium dihydrogen phosphate (ADP), diammonium hydrogen phosphate, ammonium acetate, sodium dihydrogen phosphate, potassium dihydrogen phosphate, dipotassium hydrogen phosphate, phosphoric acid, the sodium phosphate.
5, method according to claim 1 and 2 is characterized in that: starting material is any in nitrogenous fertilizer, phosphate fertilizer, potash fertilizer and compound fertilizer thereof or the mixed fertilizer.
6, method according to claim 1 and 2 is characterized in that: starting material is any in mineral sources agricultural chemicals, biogenic pesticide and the chemical pesticide.
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| CN2009100672262A CN101653114B (en) | 2009-07-03 | 2009-07-03 | Hydroxyl apatite pesticide and fertilizer slow release complex prepared by one step synthesis |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106431750A (en) * | 2016-09-12 | 2017-02-22 | 巢湖春友种业科技有限公司 | Hydroxyapatite-modified biochar fertilizer and preparation method thereof |
| CN106699384A (en) * | 2016-12-28 | 2017-05-24 | 滁州市施集赵洼茶厂 | Active organic tea tree fertilizer capable of adsorbing liquid fermented products and preparation method of active organic tea tree fertilizer |
| CN106922654A (en) * | 2016-12-31 | 2017-07-07 | 新昌县迪斯曼科技有限公司 | One-step synthesis prepare hydroxyapatite pesticide, fertilizer slow release complex |
| CN111990085A (en) * | 2020-09-04 | 2020-11-27 | 浙江茂源林业工程有限公司 | Method for grafting Chinese torreya to Chinese torreya tree, fertilizer and preparation method thereof |
| CN113943192A (en) * | 2021-12-06 | 2022-01-18 | 厦门紫金矿冶技术有限公司 | Nano hybrid N, P slow release fertilizer and preparation method thereof |
-
2009
- 2009-07-03 CN CN2009100672262A patent/CN101653114B/en not_active Expired - Fee Related
Non-Patent Citations (2)
| Title |
|---|
| 吴丽艳等: "羟基磷灰石/药物纳米复合物的制备研究", 《吉林省第六届生命科学大型学术报告会论文集》 * |
| 滕利荣等: "羟基磷灰石纳米粒子作为蛋白类缓释药物载体的应用", 《吉林大学学报(工学版)》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106431750A (en) * | 2016-09-12 | 2017-02-22 | 巢湖春友种业科技有限公司 | Hydroxyapatite-modified biochar fertilizer and preparation method thereof |
| CN106699384A (en) * | 2016-12-28 | 2017-05-24 | 滁州市施集赵洼茶厂 | Active organic tea tree fertilizer capable of adsorbing liquid fermented products and preparation method of active organic tea tree fertilizer |
| CN106922654A (en) * | 2016-12-31 | 2017-07-07 | 新昌县迪斯曼科技有限公司 | One-step synthesis prepare hydroxyapatite pesticide, fertilizer slow release complex |
| CN111990085A (en) * | 2020-09-04 | 2020-11-27 | 浙江茂源林业工程有限公司 | Method for grafting Chinese torreya to Chinese torreya tree, fertilizer and preparation method thereof |
| CN111990085B (en) * | 2020-09-04 | 2021-12-24 | 浙江茂源林业工程有限公司 | Method for grafting Chinese torreya to Chinese torreya tree, fertilizer and preparation method thereof |
| CN113943192A (en) * | 2021-12-06 | 2022-01-18 | 厦门紫金矿冶技术有限公司 | Nano hybrid N, P slow release fertilizer and preparation method thereof |
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